四磺酸基酞菁锌在水和非水溶剂中的电化学性质研究

在非水溶剂（二甲基亚砜（ＤＭＳＯ）及Ｎ,Ｎ＿二甲基甲酰胺（ＤＭＦ））中的伏安曲线．呈现三对电流峰,表明存在三个可逆或准可逆酞菁配体的单电子转移过程,而在水溶液中则不呈现准可逆行为,且波形改变很大．此外,还比较了四磺酸基酞菁锌的水溶液在自然光和红光（６００～７００ｎｍ）照射下的循环伏安曲线,其氧化还原峰的数目和峰电位基本不变,但在红光照射下比自然光照射下的峰电流明显增大．     

Direct Trimethylsilylation of Phenanthrene and its Products—An Abnormal Silylation of Phenanthrene

Direct trimethylsilylation¹⁾ of phenanthrene in different molar ratio of phenanthrene/sodium/trimethylchlorosilane is reported and discussed. Instead of the aromatic silyl compounds, such as 9-trimethylsilylphenanthrene (V), the hydroaromatic silyl compounds, such as 9, 10–bis (trimethylsilyl)-9, 10-dihydrophenanthrene (I) were obtained preferentially. Structure of these compounds are characterized and discussed. These silylated products have a general trend to change their properties during long time storage in the atmosphere under exposure to light. A significant difference of chemical shifts between silylated aromatic compound (V) and silylated hydroaromatic compound (I-IV) was observed.     

Experimental and computational studies of intracomplex reactions in Mg+(primary, secondary alkylamine) complexes induced by photoexcitation of Mg+

We report herein a comprehensive study of photoinduced reactions in complexes of Mg+ with primary (n-propyl- and isopropylamine) and secondary amines (dipropyl- and diisopropylamine) in the spectral range of 230-440 nm. Similar to the methyl- and ethylamine complexes studied previously, N-H bond activation of these complexes is very unfavorable. Instead, the C(alpha)-C, C-N, and C(alpha)-H bond-cleavage photoproducts are observed after photoexcitation of the Mg+ complexes (3(2)P<--3(2)S). For Mg+(primary amine) complexes, for example, Mg+-NH2CH2CH2CH3, and Mg+-NH2CH(CH3)2, the photoproducts resulting from C(alpha)--C rupture prevail after P(z) and charge-transfer excitations, whereas the Mg+ photofragment is predominant upon P(x,y) excitation. However, with further N-alkyl substitution, as in Mg+(secondary amine) complexes, for example, Mg+-NH(CH2CH2CH3)2 and Mg+-NH[CH(CH3)2]2, a novel intracomplex C-C coupling photoreaction dominates on P(x,y) excitation of Mg+, which is believed to arise from Mg+* insertion into the C-N bond. With P(z) and charge-transfer excitation, the Mg-R elimination photoproducts, arising from C(alpha)-C bond cleavage, predominate. The energetics and possible mechanisms of the intracomplex photoreactions are analyzed in detail with the help of extensive quantum mechanics calculations.     

Coriatone and corianlactone, two novel sesquiterpenes from Coriaria nepalensis

Both coriatone (1). a novel highly oxygenated picrotoxane-type sesquiterpene, and corianlactone (2). with an unprecedented sesquiterpene basic skeleton, named coriane, were isolated from Coriaria nepalensis Wall. The structures of 1 and 2 were determined by analysis of their two-dimensional NMR data, and the structure of 2 was confirmed by X-ray analysis. Compounds 1 and 2 showed no remarkable inhibitory activity toward K(562) cells. They are cytotoxic with IC(50) > 50 microg/mL (cis-platinim: IC(50) = 0.49 microg/mL).     

Remarkably efficient oxidative coupling of N,N-dialkylarylamines in water mediated by cerium(IV) ammonium nitrate

A highly effective, economical, and environmentally friendly method using of CAN as oxidant and water as solvent for oxidative coupling of N,N-dialkylarylamines was reported.     

Direct determination of cadmium at parts-per-billion level in waters by derivative atomic absorption spectrometry using atom trapping technique

A method has been described for the direct determinations of trace cadmium using derivative atom trapping flame atomic absorption spectrometry with an improved water-cooled stainless steel trapping equipment. The characteristic concentration (gave a derivative absorbance of 0.0044) and detection limit (3sigma) of cadmium were 0.028 and 0.02 ng ml(-1) when collecting for a 1 min, respectively, which were 992 and 145-fold better than those of the conventional flame atomic absorption spectrometry. The detection limit and sensitivity of the proposed method for a 2 min collection time were 1 and 2 orders of magnitude higher than those of conventional flame atomic absorption spectrometry. The present method was applied to the determinations of cadmium in water samples with a recovery range of 91 approximately 111% and a relative standard deviation of 4.7 approximately 5.6%.     

双核银络合物[Ag_2(dppm)_2(Py)_2(μ-Cl)]ClO_4的合成与结构

二-(二苯基膦)甲烷(dppm)是一种易与金属形成多核络合物的有机膦配体。我们用dppm作为配体合成了一系列银的多核络合物,并对其结构进行了研究。本文报导了其中一个双核化合物[Ag_2(dppm)_2(Py)_2(μ-Cl)]ClO_4的合成及晶体结构、分子结构的测定。     

不同热管工质对热管冷却反应堆堆芯物理参数的影响与分析

热管冷却反应堆采用非能动传热技术,热响应速度快,可避免堆芯单点失效,具有功率密度大、寿命长、环境适应性强、工作性能稳定等特点,是目前空间核反应堆研究的热点。本文基于清华大学开发的反应堆蒙特卡洛中子输运程序RMC (Reactor Monte Carlo code),以美国爱荷华国家实验室(Idaho National Laboratory, INL)设计的热管冷却反应堆INL Design A为研究对象,选取3种热管工质开展热管冷却反应堆堆芯物理计算。计算结果表明：锂热管工质不仅拥有很好的热物性参数,并且使用锂热管工质的热管冷却反应堆缓发中子有效份额最大、中子能谱较硬、燃耗反应性损失最小、增殖性能最佳,有利于热管冷却反应堆堆芯小型化与长寿命。因此,推荐锂为热管冷却反应堆的热管工质。     

震区中小跨径桥梁墩柱配筋率取值范围

为研究配筋率对钢筋混凝土桥梁延性抗震性能的影响,并在不同设防烈度对主筋配筋率的合理取值进行细分。以钢筋混凝土桥梁为研究对象,通过拟静力模型试验与有限元数值分析的方法,研究竖向钢筋(主筋)配筋率对桥墩延性的影响,提出典型桥墩的多级性能水平量化指标;并探究在氯离子侵蚀的恶劣环境下,不同配筋率对桥梁抗震性能所带来的影响,从而对氯离子侵蚀环境下的震区中小跨径桥梁墩柱配筋率取值范围提供参考建议。结果表明：考虑氯离子侵蚀作用下的恢复力模型能够较好地反映刚度的退化特性,墩柱的最佳配筋率取值范围为1.11%～2.72%;当加速度为0.3g(g为重力加速度)时,仅从配筋率的角度已无法满足墩柱的损伤指标,建议采用减隔震体系进行抗震设计,如采用延性体系时配筋率不得小于2.64%。研究结果可为中小跨径连续桥梁抗震设计提供参考。     

四硝基酞菁合钴化学修饰电极的制备及对氧的电催化还原

合成了4,4′,4″,4″′—四硝基酞菁合钴(Ⅱ),并进行了表征,用不可逆吸附法制备了该化合物为修饰物的化学修饰电极,以光电子能谱法进行了表面表征。并研究了分子氧在该化学修饰电极上的电化学行为,发现该化学修饰电极对氧的还原有明显的电催化作用。